Kinetics and mechanism of triclocarban degradation by the chlorination process: Theoretical calculation and experimental verification.

Triclocarban (TCC) is an antimicrobial agent commonly used in many household and personal care products, and has been found persistent in the aquatic environment. Here we elucidate the kinetics and mechanism of TCC degradation during chlorination process by density functional theory (DFT) calculation and experimental verification. Results showed that hypochlorous acid (HOCl)/hypochlorite (OCl-) reacted with TCC via Cl-substitution, OH-substitution and C-N bond cleavage pathways. The reactivity of OCl- (2.80 × 10-7 M-1 s-1) with TCC was extremely low and HOCl (1.96 M-1 s-1) played the dominant role in TCC chlorination process. The N site of TCC was the most reactive site for chlorination. The second-order rate constants, which are determined using density functional theory (DFT) (kTCC-chlorineC, 1.96 M-1 s-1), can be separated into reaction rate constants related to the reactions of HOCl and OCl- with different isomers of TCC (TCC2 and TCC6). The obtained kTCC-chlorineC was consistent with the experimental determined second-order rate constant (kTCC-chlorineE, 3.70 M-1 s-1) in chlorination process. Eight transformation products (TP348, TP382, TP127, TP161, TP195, TP330, TP204, and TP296) were experimentally detected for chlorination of TCC, which could also be predicted by DFT calculation. Explicit water molecules participated in the chlorination reaction by transmitting the proton and connecting with TCC, HOCl/OCl- and other H2O molecules, and obviously reduced the energy barrier of chlorination.

Revisiting photocyclization of the donor-acceptor stenhouse adduct: missing pieces in the mechanistic jigsaw discovered.

Donor-acceptor Stenhouse adducts (DASA) have recently emerged as a class of visible-light-induced photochromic molecular switches, but their photocyclization mechanism remains puzzling and incomplete. In this work, we carried out MS-CASPT2//SA-CASSCF calculations to reveal the complete mechanism of the dominant channels and possible side reactions. We found that a new thermal-then-photo isomerization channel, i.e., EEZ → EZZ → EZE, other than the commonly accepted EEZ → EEE → EZE channel, is dominant in the initial step. Besides, our calculations rationalized why the expected byproducts ZEZ and ZEE are unobserved and proposed a competitive stepwise channel for the final ring-closure step. The findings here redraw the mechanistic picture of the DASA reaction by better accounting for experimental observations, and more importantly, provide critical physical insight in understanding the interplay between thermal- and photo-induced processes widely present in photochemical synthesis and reactions.

A novel all-nitrogen molecular crystal N16 as a promising high-energy-density material.

All-nitrogen solids, if successfully synthesized, are ideal high-energy-density materials because they store a great amount of energy and produce only harmless N2 gas upon decomposition. Currently, the only method to obtain all-nitrogen solids is to apply high pressure to N2 crystals. However, products such as cg-N tend to decompose upon releasing the pressure. Compared to covalent solids, molecular crystals are more likely to remain stable during decompression because they can relax the strain by increasing the intermolecular distances. The challenge of such a route is to find a molecular crystal that can attain a favorable phase under elevated pressure. In this work, we show, by designing a novel N16 molecule (tripentazolylamine) and examining its crystal structures under a series of pressures, that the aromatic units and high molecular symmetry are the key factors to achieving an all-nitrogen molecular crystal. Density functional calculations and structural studies reveal that this new all-nitrogen molecular crystal exhibits a particularly slow enthalpy increase with pressure due to the highly efficient crystal packing of its highly symmetric molecules. Vibration mode calculations and molecular dynamics (MD) simulations show that N16 crystals are metastable at ambient pressure and could remain inactive up to 400 K. The initial reaction steps of the decomposition are calculated by following the pathway of the concerted excision of N2 from the N5 group as revealed by the MD simulations.

Kinetics and Mechanism of Degradation of Reactive Radical-Mediated Probe Compounds by the UV/Chlorine Process: Theoretical Calculation and Experimental Verification.

The UV/chlorine process, by combining chlorination with UV irradiation, has been recently considered as a highly efficient advanced oxidation process (AOP) technology in water treatment. Nitrobenzene (NB), benzoic acid (BA), and p-chlorobenzoic acid (pCBA) are widely used as model probe compounds in the UV/chlorine system to calculate the second-order rate constants of the specific radical reaction with target contaminates by a competitive kinetics method. A comprehensive understanding of probe compounds' reaction mechanism with reactive radicals is critical for investigation of the UV/chlorine reaction system. Here, we evaluated the radical-mediated reaction kinetics and mechanism of NB, BA, and pCBA in the UV/chlorine process using theoretical calculations and experimental studies. The main reactive radicals •OH, •ClO, and •Cl in the UV/chlorine process for the initial reaction with NB, BA, and pCBA can be explained by H-abstraction and addition pathways. The ΔE 0,≠ values for the •OH reaction with NB, BA, and pCBA were in the range of 5.0-8.0, 3.7-8.2, and 3.4-8.2 kcal mol-1, respectively. The ΔE 0,≠ values for •ClO and •Cl reactions with these three probe compounds were higher than those of •OH, indicating slower •ClO- and •Cl-initiated reactions than that of the •OH-initiated reaction. The theoretically calculated radical-mediated reaction kinetic rate constants (k CP C) for NB, BA, and pCBA were 4.58 × 10-3, 1.28 × 10-2, and 1.6 × 10-2 s-1, respectively, which was consistent with the experimentally determined pseudo-first-order rate constant (k CP RR) in the UV/chlorine process. Interestingly, theoretical calculations showed that •ClO and •Cl played an important role in subsequent reactions of NB-OH radicals, converting to hydroxylated and chlorinated products, which were further confirmed by experimental products' identification. The findings from this study indicated that quantum chemistry calculations provide an effective means to investigate the reaction kinetics and mechanism of chemicals in the UV/chlorine process.

Degradation pathways of penthiopyrad by δ-MnO2 mediated processes: a combined density functional theory and experimental study.

Penthiopyrad is a widely used succinate dehydrogenase inhibitor (SDHI) fungicide and frequently detected in natural environments. In order to better understand its fate in natural systems, the degradation of penthiopyrad by manganese dioxide (MnO2) was investigated in this study. The results show that penthiopyrad is rapidly degraded in the δ-MnO2 system. Moreover, density functional theory (DFT) calculations reveal that the atoms of C18, C12, and S1 in penthiopyrad have relatively high reactive active sites. The degradation products mainly include sulfoxides, sulfones, and diketone. A sulfoxide and sulfone are formed by the oxidation of the thioether group, and diketone is formed by the oxidation of the olefin group, respectively. Based on the DFT calculations and degradation products, the degradation pathway of penthiopyrad by MnO2 is proposed. This study also reveals that the degradation of penthiopyrad by δ-MnO2 is affected by various environmental factors. A warm environment, low pH, and co-existing humic acid are beneficial to the degradation of penthiopyrad in the δ-MnO2 system, whereas, co-existing metal cations inhibit penthiopyrad degradation. This result provides theoretical guidance for predicting the potential fate of penthiopyrad in natural environments.

Cobalt(II)-Catalyzed [4+2] Annulation of Picolinamides with Alkynes via C-H Bond Activation.

A cobalt(II)-catalyzed [4+2] annulation of picolinamides with alkynes via C-H bond activation has been developed. The operationally simple annulation reaction allows for the synthesis of acyl-substituted 1H-benzoquinoline bearing multiple aromatic rings (up to 96 % yield) without co-oxidant or other oxidation factors under mild conditions. Several control experiments were carried out. This practical [4+2] annulation provides an efficient route to access highly functionalized compounds.

Predicting the Feasibility of Copper(I)-Catalyzed Alkyne-Azide Cycloaddition Reactions Using a Recurrent Neural Network with a Self-Attention Mechanism.

The copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction, a major click chemistry reaction, is widely employed in drug discovery and chemical biology. However, the success rate of the CuAAC reaction is not satisfactory as expected, and in order to improve its performance, we developed a recurrent neural network (RNN) model to predict its feasibility. First, we designed and synthesized a structurally diverse library of 700 compounds with the CuAAC reaction to obtain experimental data. Then, using reaction SMILES as input, we generated a bidirectional long-short-term memory with a self-attention mechanism (BiLSTM-SA) model. Our best prediction model has total accuracy of 80%. With the self-attention mechanism, adverse substructures responsible for negative reactions were recognized and derived as quantitative descriptors. Density functional theory investigations were conducted to provide evidence for the correlation between bromo-α-C hybrid types and the success rate of the reaction. Quantitative descriptors combined with RDKit descriptors were fed to three machine learning models, a support vector machine, random forest, and logistic regression, and resulted in improved performance. The BiLSTM-SA model for predicting the feasibility of the CuAAC reaction is superior to other conventional learning methods and advances heuristic chemical rules.

Nano-makisu: highly anisotropic two-dimensional carbon allotropes made by weaving together nanotubes.

Graphene and carbon nanotubes (CNT) are the representatives of two-dimensional (2D) and one-dimensional (1D) forms of carbon, both exhibiting unique geometric structures and peculiar physical and chemical properties. Herein, we propose a family or series of 2D carbon-based highly anisotropic Dirac materials by weaving together an array of CNTs by direct C-C bonds or by graphene ribbons. By employing first-principles calculations, we demonstrate that these nano-makisus are thermally and dynamically stable and possess unique electronic properties. These 2D carbon allotropes are all metals and some nano-makisus show largely anisotropic Dirac cones, causing very different transport properties for the Dirac fermions along different directions. The Fermi velocities in the kx direction could be ∼170 times higher than those in the ky direction, which is the strongest anisotropy among 2D carbon allotropes to the best of our knowledge. This intriguing feature of the electronic structure has only been observed in heavy element materials with strong spin-orbit coupling. These results indicate that carbon based materials may have much broader applications in future nanoelectronics.

Side-Chain Polymers as Dopant-Free Hole-Transporting Materials for Perovskite Solar Cells-The Impact of Substituents' Positions in Carbazole on Device Performance.

Side-chain polymers have the potential to be excellent dopant-free hole-transporting materials (HTMs) for perovskite solar cells (PSCs) because of their unique characteristics, such as tunable energy levels, high charge mobility, good solubility, and excellent film-forming ability. However, there has been less research focusing on side-chain polymers for PSCs. Here, two side-chain polystyrenes with triphenylamine substituents on carbazole moieties were designed and characterized. The properties of the side-chain polymers were tuned finely, including the photophysical and electrochemical properties and charge mobilities, by changing the positions of triphenylamine substituents on carbazole. Owing to the higher mobility and charge extraction ability, the polymer P2 with the triphenylamine substituent on the 3,6-positions of the carbazole unit showed higher performance with power conversion efficiency (PCE) of 18.45%, which was much higher than the PCE (16.78%) of P1 with 2,7-positions substituted. These results clearly demonstrated that side-chain polymers can act as promising HTMs for PSC applications and the performance of side-chain polymers could be optimized by carefully tuning the structure of the monomer, which provides a new strategy to design new kinds of side-chain polymers and obtain high-performance dopant-free HTMs.

Mechanism of Synergistic Effect on Electron Transfer over Co-Ce/MCM-48 during Ozonation of Pharmaceuticals in Water.

The same amount of metal was deposited on the surface of three-dimensional mesoporous MCM-48 by a facile impregnation-calcination method for catalytic ozonation of pharmaceutical and personal-care products in the liquid phase. At 120 min reaction time, Co/MCM-48 and Ce/MCM-48 showed 46.6 and 63.8% mineralization for clofibric acid (CA) degradation, respectively. Less than 33% mineralization was achieved with Co/MCM-48 and Ce/MCM-48 during sulfamethazine (SMZ) ozonation. In the presence of monometallic oxides modified MCM-48 catalysts, total organic carbon (TOC) removal of diclofenac sodium (DCF) was around 80%. The composite Co-Ce/MCM-48 catalyst exhibited significantly higher activity in terms of TOC removal of CA (83.6%), SMZ (51.7%) and DCF (86.8%). Co-Ce/MCM-48 inhibited efficiently the accumulation of small molecular carboxyl acids during ozonation. A detailed research was conducted to detect the nature of material structure and mechanism of catalytic ozonation by using a series of characterizations. The main reaction pathway of CA was determined by the analysis of liquid chromatography-mass spectrometry, in line with the results of frontier electron density calculations that reactive oxygen species (ROSs) were easy to attack negative regions of pharmaceuticals. The Si-O-Si, Co···HO-Si-O-Si-OH···Ce, and O3···Co-HO-Si-O-Si-OH···Ce-OH···O3 basic units in catalysts were constructed to detect the orbit-energy-level difference. The results revealed that a synergistic effect existed at the interface between cobalt and cerium oxides over MCM-48, which facilitated the ROSs sequence in solution with ozone. Therefore, the multivalence redox coupling of Ce4+/Ce3+ and Co3+/Co2+ along with electron transfer played an important role in catalytic ozonation process.

Planar tetracoordinate carbon species CLi3E with 12-valence-electrons.

We exhibit theoretically a series of 12-valence-electron pentaatomic species CLi3E (E = N, P, As, Sb, Bi) and CLi3E(+) (E = O, S, Se, Te, Po). The analyses of potential energy surfaces indicate that the C2v structures with a planar tetracoordinate carbon are the global minimum in these species except for E = N, P. A localized C[double bond, length as m-dash]E double bond is found in the planar tetracoordinate carbon species. The molecular orbitals and the valence populations reveal that the C[double bond, length as m-dash]E double bonds in CLi3E are different from those in CLi3E(+). The thermodynamic and kinetic calculations show that some of the planar tetracoordinate carbon species are stable and are likely to exist in the gas phase.

Spectroscopic analysis and in vitro imaging applications of a pH responsive AIE sensor with a two-input inhibit function.

A novel terpyridine derivative formed stable aggregates in aqueous media (DMSO/H2O = 1/99) with dramatically enhanced fluorescence compared to its organic solution. Moreover, the ultra-violet absorption spectra also demonstrated specific responses to the incorporation of water. The yellow emission at 557 nm changed to a solution with intense greenish luminescence only in the presence of protons and it conformed to a molecular logic gate with a two-input INHIBIT function. This molecular-based material could permeate into live cells and remain undissociated in the cytoplasm. The new aggregation induced emission (AIE) pH type bio-probe permitted easy collection of yellow luminescence images on a fluorescent microscope. As designed, it displayed striking green emission in organelles at low internal pH. This feature enabled the self-assembled structure to have a whole new function for the pH detection within the field of cell imaging.

Fabrication of SnO2-reduced graphite oxide monolayer-ordered porous film gas sensor with tunable sensitivity through ultra-violet light irradiation.

A new graphene-based composite structure, monolayer-ordered macroporous film composed of a layer of orderly arranged macropores, was reported. As an example, SnO2-reduced graphite oxide monolayer-ordered macroporous film was fabricated on a ceramic tube substrate under the irradiation of ultra-violet light (UV), by taking the latex microsphere two-dimensional colloid crystal as a template. Graphite oxide sheets dispersed in SnSO4 aqueous solution exhibited excellent affinity with template microspheres and were in situ incorporated into the pore walls during UV-induced growth of SnO2. The growing and the as-formed SnO2, just like other photocatalytic semiconductor, could be excited to produce electrons and holes under UV irradiation. Electrons reduced GO and holes adsorbed corresponding negative ions, which changed the properties of the composite film. This film was directly used as gas-sensor and was able to display high sensitivity in detecting ethanol gas. More interestingly, on the basis of SnO2-induced photochemical behaviours, this sensor demonstrated tunable sensitivity when UV irradiation time was controlled during the fabrication process and post in water, respectively. This study provides efficient ways of conducting the in situ fabrication of a semiconductor-reduced graphite oxide film device with uniform surface structure and controllable properties.

Electric field effects on the intermolecular interactions in water whiskers: insight from structures, energetics, and properties.

Modulation of intermolecular interactions in response to external electric fields could be fundamental to the formation of unusual forms of water, such as water whiskers. However, a detailed understanding of the nature of intermolecular interactions in such systems is lacking. In this paper, we present novel theoretical results based on electron correlation calculations regarding the nature of H-bonds in water whiskers, which is revealed by studying their evolution under external electric fields with various field strengths. We find that the water whiskers consisting of 2-7 water molecules all have a chain-length dependent critical electric field. Under the critical electric field, the most compact chain structures are obtained, featuring very strong H-bonds, herein referred to as covalent H-bonds. In the case of a water dimer whisker, the bond length of the novel covalent H-bond shortens by 25%, the covalent bond order increases by 9 times, and accordingly the H-bond energy is strengthened by 5 times compared to the normal H-bond in a (H2O)2 cluster. Below the critical electric field, it is observed that, with increasing field strength, H-bonding orbitals display gradual evolutions in the orbital energy, orbital ordering, and orbital nature (i.e., from typical π-style orbital to unusual σ-style double H-bonding orbital). We also show that, beyond the critical electric field, a single water whisker may disintegrate to form a loosely bound zwitterionic chain due to a relay-style proton transfer, whereas two water whiskers may undergo intermolecular cross-linking to form a quasi-two-dimensional water network. Overall, these results help shed new insight on the effects of electric fields on water whisker formation.

Photochemistry-based method for the fabrication of SnO(2) monolayer ordered porous films with size-tunable surface pores for direct application in resistive-type gas sensor.

A new photochemistry-based method was introduced for fabricating SnO2 monolayer ordered porous films with size-tunable surface pores on ceramic tubes used for gas sensors. The growth of the spherical pore walls was controlled by two times irradiation of the ultraviolet light using polystyrene microsphere two-dimensional colloidal crystal as a template. The surface pore size of the final obtained porous films was well tuned by changing the second irradiation time rather than replacing the template microspheres. The monolayer ordered porous films on the tubes were directly used, for the first time, as gas sensors. The sensitivity of the sensor depended on the surface pore size and was carefully analyzed by ethanol gas detection. The sensor also exhibited short response-recovery time and long-term stability at lower than 300 °C in practical applications. Therefore, this study opens up a kind of construction method for gas sensors, provides a new strategy for controlling the surface pore size of the monolayer ordered porous film, and introduces a new type of sensitivity-controllable gas sensor.

Platinum(II)-catalyzed asymmetric ring-opening addition of arylboronic acids to oxabenzonorbornadienes.

A new platinum(II)-catalyzed asymmetric ring-opening addition of arylboronic acids to oxabenzonorbornadienes was developed, which afforded the corresponding cis-2-aryl-1,2-dihydronaphthalen-1-ol products in high yields (up to 97%) with moderate to good enantioselectivities (up to 89% ee) under very mild conditions. The effects of various ligands, catalyst loading, bases, solvents, and temperatures on the yield and enantioselectivity of the reaction were also investigated. The cis configuration of product 2m was confirmed by X-ray diffraction analysis. A potential mechanism for the present catalytic reaction is proposed.

Theoretical study on the reaction mechanisms of CH3O- with O2(X3Σ(g)-) and O2(a1Δ(g)).

The detailed potential energy surfaces (PESs) of poorly understood ion-molecule reactions of CH(3)O(-) with O(2)(X(3)Σ(g)(-)) and O(2)(a(1)Δ(g)) are accounted for by the density functional theory and ab initio of QCISD and CCSD(T) (single-point) theoretical levels with 6-311++G(d,p) and 6-311++G(3df,2pd) basis sets for the first time. For the reaction of CH(3)O(-) with O(2)(X(3)Σ(g)(-)) ((3)R), it is shown that a hydrogen-bonded complex (3)1 is initially formed on the triplet PES, which is 1.8 kcal/mol above reactants (3)R at the CCSD(T)//QCISD level, from which all the products P(1)-P(8) can be generated. As to the reaction of CH(3)O(-) with O(2)(a(1)Δ(g)) ((1)R), it is found that the two energetically low-lying complexes of (1)1(-31.5 kcal/mol) and (1)2(-24.1 kcal/mol) are initiated on the singlet PES. Starting from them, a total of seven products may be possible, that is, besides P(1), P(2), P(3), P(4), and P(8), which are the same as on the triplet PES, there exist also another two products, P(9) and P(10). For both reactions, taking the thermodynamics and kinetics into consideration, the hydride-transfer species P(1)(CH(2)O + HO(2)(-)) should be the most favorable product followed by P(8)(e + CH(2)O + HO(2)), which is a secondary product of electron-detachment from P(1), and the generation of endothermic P(7)(17.7 kcal/mol) for the reaction of CH(3)O(-) with O(2)(X(3)Σ(g)(-)) is also possible at high temperature, whereas the remaining products are negligible. The measured branching ratio of products for CH(3)O(-) with O(2)(X(3)Σ(g)(-)) by Midey et al. is 0.85:0.15 for P(1) and P(8), and that of CH(3)O(-) with O(2)(a(1)Δ(g)) is 0.52:0.48 with more P(8), which can be rationalized by our theoretical results that P(8) on the triplet PES is 4.9 kcal/mol above (3)R, whereas both P(1) and P(8) on the singlet PES are very low-lying at 45.6 and 25.2 kcal/mol below (1)R energetically. The measured total reaction rate constant of CH(3)O(-) with O(2)(a(1)Δ(g)) is k = 6.9 × 10(-10) cm(3) s(-1) at 300 K, which is larger than that of k = 1.1 × 10(-12) cm(3) s(-1) for the reaction of CH(3)O(-) with O(2)(X(3)Σ(g)(-)). This is understandable because both P(1) and P(8) on the singlet PES can be generated barrierlessly, whereas to give all the products on the triplet PES has to pass the barrier of (3)1(1.8 kcal/mol) at the CCSD(T)//QCISD level. It is expected that the present theoretical study may be helpful for understanding the reaction mechanisms related to CH(3)O(-) and even CH(3)S(-).

Gelification: an effective measure for achieving differently sized biocompatible Fe3O4 nanocrystals through a single preparation recipe.

Biocompatible Fe(3)O(4) nanocrystals were synthesized through the pyrolysis of ferric acetylacetonate (Fe(acac)(3)) in diphenyl oxide, in the presence of α,ω-dicarboxyl-terminated polyethylene glycol (HOOC-PEG-COOH) and oleylamine. Unusual gelification phenomena were observed from the aliquots extracted at different reaction stages after they were cooled to room temperature. By reaction time, the average size of the Fe(3)O(4) nanocrystals was tuned from 5.8 to 11.7 nm with an equilibrium size around 11.3 nm. By increasing the gelification degree of the stock solution, the equilibrium size of the Fe(3)O(4) nanocrystals was further increased from 11.3 to 18.9 nm. The underlying gel formation mechanism was investigated by using ultraviolet-visible absorption spectroscopy and Fourier transform infrared spectroscopy. The results suggest that the complexation between HOOC-PEG-COOH and Fe(acac)(3), with the help of oleylamine, results in large molecular networks, which are responsible for the gelification of the stock solution, while the interaction between the fragment of the molecular network and Fe(3)O(4) nanocrystal is responsible for the second gelification process observed during the early stage of reflux. To further investigate the particle growth behavior, small molecules released during the preparation were collected and analyzed by using photoelectron spectroscopy/photoionization mass spectroscopy (PES/PIMS). It was demonstrated that the pyrolysis of the Fe precursor is strongly correlated with the particle growth process. Further numerical simulations reveal that the first gelification process induced by the complexation between HOOC-PEG-COOH and Fe(acac)(3) largely alters the pyrolysis behavior of the Fe precursor; consequently, the equilibrium size of the resultant Fe(3)O(4) nanocrystals can effectively be tuned by the gelification degree of the stock solution.

Degradation of decabromodiphenyl ether by nano zero-valent iron immobilized in mesoporous silica microspheres.

The agglomeration of nanoparticles reduces the surface area and reactivity of nano zero-valent iron (NZVI). In this paper, highly dispersive and reactive NZVI immobilized in mesoporous silica microspheres covered with FeOOH was synthesized to form reactive mesoporous silica microspheres (SiO(2)@FeOOH@Fe). The characteristics of SiO(2)@FeOOH@Fe were analyzed by transmission electron microscopy, Fourier transform infrared spectroscopy simultaneous thermal analysis, X-ray photoelectron spectroscopy, and Brunnaer-Emmett-Teller surface area analysis. The mean particle size of the reactive mesoporous silica microspheres was 450 nm, and its specific surface area was 383.477 m(2) g(-1). The degradation of dcabromodiphenyl ether (BDE209) was followed pseudo-first-order kinetics, and the observed reaction rate constant could be improved by increasing the SiO(2)@FeOOH@Fe dosage and by decreasing the initial BDE209 concentration. The stability and longevity of the immobilized Fe nanoparticles were evaluated by repeatedly renewing the BDE209 solution in the reactor. The stable degradation of BDE209 by SiO(2)@FeOOH@Fe was observed within 10 cycles. Agglomeration-resistance and magnetic separation of SiO(2)@FeOOH@Fe were also performed. The improved dispersion of SiO(2)@FeOOH@Fe in solution after one-month storage and its good performance in magnetic separation indicated that SiO(2)@FeOOH@Fe has the potential to be efficiently applied to environmental remediation.

Novel molecularly imprinted microsphere using a single chiral monomer and chirality-matching (S)-ketoprofen template.

We designed and synthesized a cinchonine derivative to be used as a novel chiral monomer. It was employed in a dual role of functional monomer and cross-linking monomer, displaying multi-binding sites for the template (S)-ketoprofen. Monodisperse molecularly imprinted core-shell microspheres were prepared using surface imprinting method on silica gel. The results show a substantial synergistic effect in the enantioselective recognition, confirming our initial hypothesis. Computational simulation of the monomer and template pre-arrangement strongly supports our proposed chiral recognition mechanism for the imprinted microspheres.